Fungicidal compositions

ABSTRACT

A composition for control of phytopathogenic diseases on useful plants or on propagation material thereof, that, in addition to customary inert formulation adjuvants, comprises as active ingredient a mixture of component (A) and a synergistically effective amount of component (B), wherein
     component (A) is Cyprodinil; and   component (B) a compound selected from compounds known for their fungicidal activity, is particularly effective in controlling or preventing fungal diseases of useful plants.

This application is a divisional of U.S. Ser. No. 12/088,030, filed Mar. 25, 2008, which is a 371 of International Application No. PCT/EP2006/009403 filed Sep. 27, 2006, which claims priority from EP 05021278.6 filed Sep. 29, 2005 and EP 05025915.9 filed Nov. 28, 2005; the contents of all above-named applications are incorporated herein by reference.

The present invention relates to novel fungicidal compositions for the treatment of phytopathogenic diseases of useful plants, especially phytopathogenic fungi, and to a method of controlling phytopathogenic diseases on useful plants.

EP-0-310-550 discloses Cyprodinil ((4-cyclopropyl-6-methyl-pyrimidin-2-yl)-phenyl-amine), a fungicide which is effective against a number of diseases caused by ascomycetes or deuteromycetes. On the other hand various fungicidal compounds of different chemical classes are widely known as plant fungicides for application in various crops of cultivated plants. However, crop tolerance and activity against phytopathogenic plant fungi do not always satisfy the needs of agricultural practice in many incidents and aspects.

Out of the above-mentioned needs of agricultural practice for increased crop tolerance and/or increased activity against phytopathogenic plant fungi, there is therefore proposed in accordance with the present invention a novel synergistic composition for control of phytopathogenic diseases on useful plants or on propagation material thereof, that in addition to customary inert formulation adjuvants, comprises as active ingredient a mixture of component (A) and a synergistically effective amount of component (B), wherein

component (A) is Cyprodinil (208); and component (B) is a compound selected from Dodine (289); Chlorothalonil (142); Folpet (400); Prothioconazole (685); Boscalid (88); Proquinazid (682); Dithianon (279); Fluazinam (363); Ipconazole (468); Metrafenone; a compound of formula A-1

a compound of formula A-2

a compound of formula A-3

a compound of formula A-4

a compound of formula A-5

and a compound of formula A-6

It has now been found, surprisingly, that the active ingredient mixture according to the invention not only brings about the additive enhancement of the spectrum of action with respect to the phytopathogen to be controlled that was in principle to be expected but achieves a synergistic effect which extends the range of action of the component (A) and of the component (B) in two ways. Firstly, the rates of application of the component (A) and of the component (B) are lowered whilst the action remains equally good. Secondly, the active ingredient mixture still achieves a high degree of phytopathogen control even where the two individual components have become totally ineffective in such a low application rate range. This allows, on the one hand, a substantial broadening of the spectrum of phytopathogens that can be controlled and, on the other hand, increased safety in use.

However, besides the actual synergistic action with respect to fungicidal activity, the pesticidal compositions according to the invention can also have further surprising advantageous properties which can also be described, in a wider sense, as synergistic activity. Examples of such advantageous properties that may be mentioned are: a broadening of the spectrum of fungicidal activity to other phytopathogens, for example to resistant strains; a reduction in the rate of application of the active ingredients; synergistic activity against animal pests, such as insects or representatives of the order Acarina; a broadening of the spectrum of pesticidal activity to other animal pests, for example to resistant animal pests; adequate pest control with the aid of the compositions according to the invention, even at a rate of application at which the individual compounds are totally ineffective; advantageous behaviour during formulation and/or upon application, for example upon grinding, sieving, emulsifying, dissolving or dispensing; increased storage stability; improved stability to light; more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination.

A further aspect of the instant invention is a method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to the invention.

Cyprodinil and some components B) are described in “The Pesticide Manual” [The Pesticide Manual—A World Compendium; Thirteenth Edition; Editor: C. D. S. Tomlin; The British Crop Protection Council]. Cyprodinil and those components B) are described therein under the entry number given in round brackets hereinabove for the particular component A) or B); for example, the compound “Chlorothalonil” is described under entry number (142). All of those components A) or B) are referred to hereinabove by a so-called “common name”.

The following components B) are registered under a CAS-Reg. No.: Metrafenone (CAS 220899-03-6); the compound of formula A-1 is described in WO 98/46607 and is registered under CAS-214706-53-3; the compound of formula A-2 is described in WO 02/062759 and in WO 01/010825, is registered under CAS-Reg. No.: 325156-49-8 and is also known as Pyribencarb; the compound of formula A-3 is described in WO 00/065913 and is registered under CAS-304911-98-6; the compound of formula A-4 is described in EP-1-035-122 and is registered under CAS-291771-99-8 and CAS-291771-83-0; the compound of formula A-5 is described in WO 96/19442 and is also known as Cyflufenamid (CAS-180409-60-3); and the compound of formula A-6 is described in JP-2000-319270 and is registered under CAS-304900-25-2.

According to the instant invention component (A) and/or component (B) can be used to prepare the compositions of the invention either in the free form or as a salt or metal complex thereof.

An example of a compound, that can be used to prepare the compositions of the invention either in the free form or as a salt or metal complex thereof, is cyprodinil.

Of the acids that can be used for the preparation of salts of cyprodinil, the following may be mentioned: hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid; sulfuric acid, phosphoric acid, nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid and 1,2-naphthalene-disulfonic acid.

Metal complexes consist of the underlying organic molecule and an inorganic or organic metal salt, for example a halide, nitrate, sulfate, phosphate, acetate, trifluoroacetate, trichloroacetate, propionate, tartrate, sulfonate, salicylate, benzoate, etc., of an element of main group II, such as calcium and magnesium, and of main groups III and IV, such as aluminium, tin or lead, and of subgroups I to VIII, such as chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. Preference is given to the subgroup elements of the 4th period. The metals may have any of the different valencies in which they occur. The metal complexes can be mono- or poly-nuclear, i.e. they can contain one or more organic molecule components as ligands.

In one embodiment of the invention, cyprodinil is used in the free form to prepare the compositions of the invention.

In one embodiment of the invention, the compound of component (B) is used in the free form to prepare the compositions of the invention.

Throughout this document the expression “composition” stands for the various mixtures or combinations of components A) and B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the components A) and B) is not essential for working the present invention.

The compositions according to the invention may also comprise more than one of the active components B), if, for example, a broadening of the spectrum of phytopathogenic disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components B) with Cyprodinil. Said compositions may comprise also one or more further agrochemical active ingredients, such as herbicides, fungicides, insecticides, nematocides or plant-growth regulators.

A preferred embodiment of the present invention is represented by those compostions, wherein component B) is selected from Boscalid; Proquinazid; Dodine; Fluazinam; Ipconazole; a compound of formula A-2; a compound of formula A-3; a compound of formula A-4 and a compound of formula A-6.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is selected from Boscalid; Dodine; a compound of formula A-2 and a compound of formula A-3.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is selected from Boscalid; Dodine; Fluazinam and a compound of formula A-2.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is selected from Boscalid; Dodine and a compound of formula A-2.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Chlorothalonil.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Folpet.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Prothioconazole.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Boscalid.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Proquinazid.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Dodine.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Dithianon.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Fluazinam.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Ipconazole.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is Metrafenone.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is a compound of formula A-1.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is a compound of formula A-2.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is a compound of formula A-3.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is a compound of formula A-4.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is a compound of formula A-5.

Another preferred embodiment of the present invention is represented by those compostions, wherein component B) is a compound of formula A-6.

The compositions according to the invention are effective against harmful microorganisms, such as microorganisms, that cause phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.

The compositions according to the invention are effective especially against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella).

According to the invention “useful plants” typically comprise the following species of plants: grape vines; cereals, such as wheat, barley, rye or oats; beet, such as sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as marrows, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers. This list does not represent any limitation.

The term “useful plants” is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by δ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). An example for a truncated toxin is a truncated CryIA(b), which is expressed in the Bt11 maize from Syngenta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CryIIIA055, a cathepsin-D-recognition sequence is inserted into a CryIIIA toxin (see WO 03/018810)

Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGard Plus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CryIA(c) toxin); Bollgard I® (cotton variety that expresses a CryIA(c) toxin); Bollgard II® (cotton variety that expresses a CryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CryIIIA toxin); Nature-Gard® and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CryIA(b) toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CryIA(b) toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CryIIIA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CryIIIB(b1) toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02. 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CryIA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheit and Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “useful plants” is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called “plant disease resistance genes”, as described in WO 03/000906).

Useful plants of elevated interest in connection with present invention are cereals; soybean; rice; oil seed rape; pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes, potatoes, cucurbits and lettuce.

The term “locus” of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

The term “plant propagation material” is understood to denote generative parts of a plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion.

Preferably “plant propagation material” is understood to denote seeds.

A further aspect of the instant invention is a method of protecting natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms against attack of fungi, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a compositions according to the invention.

According to the instant invention, the term “natural substances of plant origin, which have been taken from the natural life cycle” denotes plants or parts thereof which have been harvested from the natural life cycle and which are in the freshly harvested form. Examples of such natural substances of plant origin are stalks, leafs, tubers, seeds, fruits or grains. According to the instant invention, the term “processed form of a natural substance of plant origin” is understood to denote a form of a natural substance of plant origin that is the result of a modification process. Such modification processes can be used to transform the natural substance of plant origin in a more storable form of such a substance (a storage good). Examples of such modification processes are pre-drying, moistening, crushing, comminuting, grounding, compressing or roasting. Also falling under the definition of a processed form of a natural substance of plant origin is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.

According to the instant invention, the term “natural substances of animal origin, which have been taken from the natural life cycle and/or their processed forms” is understood to denote material of animal origin such as skin, hides, leather, furs, hairs and the like.

The compositions according to the invention can prevent disadvantageous effects such as decay, discoloration or mold.

A preferred embodiment is a method of protecting natural substances of plant origin, which have been taken from the natural life cycle, and/or their processed forms against attack of fungi, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a compositions according to the invention.

A further preferred embodiment is a method of protecting fruits, preferably pomes, stone fruits, soft fruits and citrus fruits, which have been taken from the natural life cycle, and/or their processed forms, which comprises applying to said fruits and/or their processed forms a compositions according to the invention.

The compositions according to the invention may also be used in the field of protecting industrial material against attack of fungi. According to the instant invention, the term “industrial material” denotes non-live material which have been prepared for use in industry. For example, industrial materials which are intended to be protected against attack of fungi can be glues, sizes, paper, board, textiles, carpets, leather, wood, constructions, paints, plastic articles, cooling lubricants, aquaeous hydraulic fluids and other materials which can be infested with, or decomposed by, microorganisms. Cooling and heating systems, ventilation and air conditioning systems and parts of production plants, for example cooling-water circuits, which may be impaired by multiplication of microorganisms may also be mentioned from amongst the materials to be protected. The compositions according to the invention can prevent disadvantageous effects such as decay, discoloration or mold.

The compositions according to the invention may also be used in the field of protecting technical material against attack of fungi. According to the instant invention, the term “technical material” includes paper; carpets; constructions; cooling and heating systems; ventilation and air conditioning systems and the like. The compositions according to the invention can prevent disadvantageous effects such as decay, discoloration or mold.

The compositions according to the invention are particularly effective against powdery mildews; rusts; leafspot species; early blights and molds; especially against Septoria, Puccinia, Erysiphe, Rhynchosporium, Pyrenophora and Tapesia in cereals; Phakopsora in soybeans; Hemileia in coffee; Phragmidium in roses; Alternaria in potatoes, tomatoes and cucurbits; Sclerotinia in turf, vegetables, sunflower and oil seed rape; black rot, red fire, powdery mildew, grey mold and dead arm disease in vine; Botrytis cinerea in fruits; Venturia and Monilinia spp. in fruits and Penicillium spp. in fruits.

The compositions according to the invention are furthermore particularly effective against seed borne and soilborne diseases, such as Alternaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Claviceps purpurea, Cochliobolus sativus, Colletotrichum spp., Epicoccum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium subglutinans, Gaumannomyces graminis, Helminthosporium spp., Microdochium nivale, Phoma spp., Pyrenophora graminea, Pyricularia oryzae, Rhizoctonia solani, Rhizoctonia cerealis, Sclerotinia spp., Septoria spp., Sphacelotheca reilliana, Tilletia spp., Typhula incarnata, Urocystis occulta, Ustilago spp. or Verticillium spp.; in particular against pathogens of cereals, such as wheat, barley, rye or oats; maize; rice; cotton; soybean; turf; sugarbeet; oil seed rape; potatoes; pulse crops, such as peas, lentils or chickpea; and sunflower.

The compositions according to the invention are furthermore particularly effective against post harvest diseasese such as Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichum candidum, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Mucor piriformis, Penicilium italicum, Penicilium solitum, Penicillium digitatum or Penicillium expansum in particular against pathogens of fruits, such as pomefruits, for example apples and pears, stone fruits, for example peaches and plums, citrus, melons, papaya, kiwi, mango, berries, for example strawberries, avocados, pomegranates and bananas, and nuts.

The amount of a composition according to the invention to be applied, will depend on various factors, such as the compounds employed; the subject of the treatment, such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting or seed dressing; the purpose of the treatment, such as, for example prophylactic or therapeutic; the type of fungi to be controlled or the application time.

It has been found that the use of components B) in combination with Cyprodinil surprisingly and substantially enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the method of the invention is effective against a wider spectrum of such fungi that can be combated with the active ingredients of this method, when used solely.

The weight ratio of A):B) is so selected as to give a synergistic activity. In general the weight ratio of A):B) is between 2000:1 and 1:1000, preferably between 100:1 and 1:100, more preferably between 20:1 and 1:50.

The synergistic activity of the compositions according to the invention is apparent from the fact that the fungicidal activity of the composition of A)+B) is greater than the sum of the fungicidal activities of A) and B).

The method of the invention comprises applying to the useful plants, the locus thereof or propagation material thereof in admixture or separately, a composition according to the invention.

Some of said compositions according to the invention have a systemic action and can be used as foliar, soil and seed treatment fungicides.

With the compositions according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms.

The compositions according to the invention are of particular interest for controlling a large number of fungi in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.

The compositions according to the invention are applied by treating the fungi, the useful plants, the locus thereof, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials threatened by fungus attack with a compositions according to the invention.

The compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials by the fungi.

The compositions according to the invention are particularly useful for controlling the following plant diseases:

Alternaria species in fruit and vegetables, Ascochyta species in pulse crops, Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes, Cercospora arachidicola in peanuts, Cochliobolus sativus in cereals, Colletotrichum species in pulse crops, Erysiphe species in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Fusarium species in cereals and maize, Gäumannomyces graminis in cereals and lawns, Helminthosporium species in maize, rice and potatoes, Hemileia vastatrix on coffee, Microdochium species in wheat and rye, Phakopsora species in soybean, Puccinia species in cereals, broadleaf crops and perrenial plants, Pseudocercosporella species in cereals, Phragmidium mucronatum in roses, Podosphaera species in fruits, Pyrenophora species in barley, Pyricularia oryzae in rice, Ramularia collo-cygni in barley, Rhizoctonia species in cotton, soybean, cereals, maize, potatoes, rice and lawns, Rhynchosporium secalis in barley and rye, Sclerotinia species in lawns, lettuce, vegetables and oil seed rape, Septoria species in cereals, soybean and vegetables, Sphacelotheca reilliana in maize, Tilletia species in cereals, Uncinula necator, Guignardia bidwellii and Phomopsis viticola in vines, Urocystis occulta in rye, Ustilago species in cereals and maize, Venturia species in fruits, Monilinia species on fruits, Penicillium species on citrus and apples.

When applied to the useful plants Cyprodinil is applied at a rate of 5 to 2000 g a.i./ha, particularly 10 to 1000 g a.i./ha, e.g. 15, 25, 50, 300, 400, 500, 600 or 750 g a.i./ha, in association with 1 to 5000 g a.i./ha, particularly 2 to 2000 g a.i./ha, e.g. 100, 250, 500, 800, 1000, 1500 g a.i./ha of a compound of component B), depending on the class of chemical employed as component B).

In agricultural practice the application rates of the compositions according to the invention depend on the type of effect desired, and typically range from 20 to 4000 g of total composition per hectare.

When the compositions according to the invention are used for treating seed, rates of 0.001 to 10 g of Cyprodinil per kg of seed, preferably from 0.01 to 1 g per kg of seed, and 0.001 to 50 g of a compound of component B), per kg of seed, preferably from 0.01 to 10 g per kg of seed, are generally sufficient.

The composition of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate inert formulation adjuvants (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to the seeds employing the compositions according to the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.

In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula I together with a compound of component B), and optionally other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.

The Examples which follow serve to illustrate the invention, “active ingredient” denoting a mixture of cyprodinil and a compound of component B) in a specific mixing ratio.

FORMULATION EXAMPLES

Wettable powders a) b) c) active ingredient 25%  50% 75% [A):B) = 1:3(a), 1:2(b), 1:1(c)] sodium lignosulfonate 5%  5% — sodium lauryl sulfate 3% —  5% sodium diisobutylnaphthalenesulfonate —  6% 10% phenol polyethylene glycol ether —  2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62%  27% —

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

Powders for dry seed treatment a) b) c) active ingredient 25% 50% 75% [A):B) = 1:3(a), 1:2(b), 1:1(c)] light mineral oil  5%  5%  5% highly dispersed silicic acid  5%  5% — Kaolin 65% 40% — Talcum — 20  

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsifiable Concentrate

active ingredient 10% [A):B) = 1:6)] octylphenol polyethylene glycol ether  3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether (35 mol of ethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Dusts a) b) c) Active ingredient  5%  6%  4% [A):B) = 1:6(a), 1:2(b), 1:10(c)] Talcum 95% — — Kaolin — 94% — mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

Extruder Granules

Active ingredient 15% [A):B) = 2:1)] sodium lignosulfonate  2% carboxymethylcellulose  1% Kaolin 82%

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated Granules

Active ingredient 8% [A):B) = 1:10)] polyethylene glycol (mol. wt. 200) 3% Kaolin 89% 

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension Concentrate

active ingredient 40% [A):B) = 1:8)] propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol of ethylene oxide)  6% Sodium lignosulfonate 10% carboxymethylcellulose  1% silicone oil (in the form of a 75% emulsion in water)  1% Water 32%

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable Concentrate for Seed Treatment

active ingredient 40%  [A):B) = 1:8)] propylene glycol 5% copolymer butanol PO/EO 2% tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (in the form of a 20% solution 0.5%  in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%  Water 45.3%  

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of cyprodinil and a compound of component B), or of each of these compounds separately, are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.

The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

A further aspect of the instant invention is a method of controlling phytopathogenic diseases on useful plants, which comprises applying to the useful plants or the locus thereof a composition according to the invention.

A further aspect of the instant invention is a method of controlling phytopathogenic diseases on useful plants, which comprises applying to the useful plants a composition according to the invention.

A further aspect of the instant invention is a method of controlling phytopathogenic diseases on cereal plants, which comprises applying to the cereal plants or to the locus thereof a composition according to the invention; preferred cereal plants are wheat or barley.

Within this embodiment, further preferred is a method of controlling phytopathogenic diseases on wheat plants, which comprises applying to the wheat plants or to the locus thereof a composition according to the invention, wherein the phytopathogenic disease is a disease selected from the group consisting of Blumeria graminis (Erysiphe graminis), Pseudocercosporella herpotrichoides, Puccinia recondita, Puccinia striiformis, Pyrenophora tritici-repentis, Septoria tritici and Tapesia spp. Within this embodiment, further preferred is a method of controlling Tapesia spp. on wheat plants, which comprises applying to the wheat plants or to the locus thereof a composition according to the invention. Within this embodiment, further preferred is a method of controlling Blumeria graminis f. sp. tritici on wheat plants, which comprises applying to the wheat plants or to the locus thereof a composition according to the invention.

Further preferred is a method of controlling phytopathogenic diseases on barley plants, which comprises applying to the barley plants or to the locus thereof a composition according to the invention, wherein the phytopathogenic disease is a disease selected from the group consisting of Blumeria graminis (Erysiphe graminis), Puccinia hordei, Puccinia striiformis, Puccinia graminis, Pyrenophora teres, Ramularia collo-cygni and Rhynchosporium secalis; preferred is a method, wherein the phytopathogenic disease is a disease selected from the group consisting of Pyrenophora teres, Ramularia collo-cygni and Rhynchosporium secalis.

Within this embodiment, further preferred is a method of controlling Ramularia collo-cygni on barley plants, which comprises applying to the barley plants or to the locus thereof a composition according to the invention.

A further aspect of the instant invention is a method of controlling phytopathogenic diseases on fruit plants or vegetable plants, which comprises applying to the fruit plants or vegetable plants or to the locus thereof a composition according to the invention; preferred fruit plants are citrus, apple, pear, strawberry or banana; preferred vegetable plants are tomato; potato; cucurbit, such as cucumber or melon; leafy vegetables, such as lettuce, spinach or celery; brassica, such as cabbage, cauliflower, oilseed rape, broccoli or brussels sprouts; allium, such as onion or leek; root crops, such as sugar beet, carrots or parsnips; or legumes, such as peas or beans.

Within this embodiment, further preferred is a method of controlling phytopathogenic diseases on fruit plants or vegetable plants, which comprises applying to the fruit plants or vegetable plants or to the locus thereof a composition according to the invention, wherein the phytopathogenic disease is a disease selected from the group consisting of Alternaria spp, Diaporthe spp, Mycosphaerella spp, Sphaerotheca spp, Sclerotinia spp, Botrytis spp, Phoma spp. Venturia spp. and Colletotrichum spp; preferred is a method, wherein the phytopathogenic disease is Alternaria spp.

Further preferred is a method of controlling phytopathogenic diseases on fruit plants, selected from citrus, apple, pear, strawberry and banana, which comprises applying to the fruit plants or to the locus thereof a composition according to the invention, wherein the phytopathogenic disease is a disease selected from the group consisting of Alternaria spp, Diaporthe spp, Mycosphaerella spp, Sphaerotheca spp, Sclerotinia spp, Botrytis spp, Phoma spp. Venturia spp. and Colletotrichum spp; preferred is a method, wherein the phytopathogenic disease is Alternaria spp.; in a further preferred embodiment, the phytopathogenic disease is Botrytis cinerea.

Further preferred is a method of controlling phytopathogenic diseases on vegetable plants, selected from tomato, potato, cucumber, lettuce, spinach, celery, cabbage, cauliflower, oilseed rape, broccoli, brussels sprouts, onion, leek, sugar beet, carrots, parsnips, peas and beans, which comprises applying to the vegetable plants or to the locus thereof a composition according to the invention, wherein the phytopathogenic disease is a disease selected from the group consisting of Alternaria spp, Diaporthe spp, Mycosphaerella spp, Sphaerotheca spp, Sclerotinia spp, Botrytis spp, Phoma spp. Venturia spp. and Colletotrichum spp; preferred is a method, wherein the phytopathogenic disease is Alternaria spp.; in a further preferred embodiment, the phytopathogenic disease is Botrytis cinerea.

A further aspect of the instant invention is a method of controlling phytopathogenic diseases on grape plants, which comprises applying to the grape plants or to the locus thereof a composition according to the invention.

Within this embodiment, further preferred is a method of controlling phytopathogenic diseases on grape plants, which comprises applying to the grape plants or to the locus thereof a composition according to the invention, wherein the phytopathogenic disease is a disease selected from the group consisting of Botrytis cinerea, Uncinula necator, Guignardia bidwellii and Plasmopara viticola; preferred is a method, wherein the phytopathogenic disease is Botrytis cinerea.

Furthermore preferred is a method of controlling Botrytis spp, preferably Botrytis cinerea, on useful plants, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, wherein the active ingredient comprises at least a mixture of Cyprodinil and Boscalid.

Furthermore preferred is a method of controlling Botrytis spp, preferably Botrytis cinerea, on useful plants, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, wherein the active ingredient comprises at least a mixture of Cyprodinil and a compound of formula A-2.

Furthermore preferred is a method of controlling Botrytis spp, preferably Botrytis cinerea, on useful plants, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, wherein the active ingredient comprises at least a mixture of Cyprodinil and a compound of formula A-4.

Furthermore preferred is a method of controlling Venturia spp on useful plants, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, wherein the active ingredient comprises at least a mixture of Cyprodinil and Dodine.

Furthermore preferred is a method of controlling Alternaria spp on useful plants, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, wherein the active ingredient comprises at least a mixture of Cyprodinil and a compound of formula A-3.

Furthermore preferred is a method of controlling Fusarium spp on useful plants, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, wherein the active ingredient comprises at least a mixture of Cyprodinil and Ipconazole.

Biological Examples

A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components.

The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S. R. “Calculating synergistic and antagonistic responses of herbicide combination”. Weeds, Vol. 15, pages 20-22; 1967):

ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture X=% action by active ingredient A) using p ppm of active ingredient Y=% action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is

$E = {X + Y - \frac{X \cdot Y}{100}}$

If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect.

Example B-1 Action Against Botrytis cinerea (Causal Fungus of Gray Mould) a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C and the inhibition of growth is determined photometrically after 3 days. The fungicide interactions in the combinations are calculated according to the COLBY method. The data generated in this experiment indicate synergy between cyprodinil and dodine and cyprodinil and pyribencarb when used in mixture with one another.

Control of Botrytis cinerea Dosage in mg active ingredient/liter final medium Observed Expected Synergistic control control benefit in Cyprodinil Dodine in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 0.5 — 26.7 — — 1 — 38.2 — — 2 — 50.5 — — 4 — 40.1 — — 8 — 51.8 — — — 4 0 — — — 8 0 — — — 16 36.3 — — 8 8 82.6 51.8 +30.8 4 4 53.1 40.1 +13.0 8 16 98.0 69.3 +28.7 4 16 97.5 61.8 +35.7 2 16 81.5 68.5 +13.0 1 8 54.5 38.2 +16.3 0.5 4 43.5 26.7 +16.8 Observed Expected Synergistic control control benefit in Cyprodinil Pyribencarb in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 0.125 — 16.7 — — 0.25 — 22.6 — — 0.5 — 21.4 — — 1 — 25.7 — — 2 — 23.2 — — 4 — 37.1 — — — 0.008 0.4 — — — 0.016 0 — — — 0.031 3.3 — — — 0.063 2.6 — — — 0.125 16.4 — — 4 0.063 51.5 38.8 +12.7 2 0.031 39.2 25.7 +13.5 4 0.125 61.3 47.4 +13.9 2 0.063 43.9 25.2 +18.7 1 0.031 32.0 28.1 +3.9 0.5 0.016 32.6 21.4 +11.2 0.25 0.016 33.6 22.6 +11.0 0.125 0.008 32.2 17.0 +15.2

b) Protective Treatment of Bean Leaf Pieces

Bean leaf disks are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 4 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to the COLBY method.

c) Protective Treatment of Whole Grape Plants

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (1×10⁶ conidia/ml) on the test plants. After an incubation period of 4 days at 21° C. and 95% relative humidity in a greenhouse the percentage leaf area covered by disease is assessed. The fungicide interactions in the combinations are calculated according to the COLBY method.

d) Protective Treatment of Whole Tomato Plants

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (1×10⁵ conidia/ml) on the test plants. After an incubation period of 4 days at 20° C. and 95% relative humidity in a growth chamber the percentage leaf area covered by disease is assessed. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-2 Action Against Septoria tritici (Causal Fungus of Septoria tritici Leaf Blotch in Wheat) a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 3 days. The fungicide interactions in the combinations are calculated according to the COLBY method.

b) Protective Treatment of Whole Plants

2 week old wheat plants cv. Riband are treated with the formulated test compound in a spray chamber. One day after application, wheat plants are inoculated by spraying a spore suspension (10×10⁵ conidia/ml) on the test plants. After an incubation period of 1 day at 23° C. and 95% relative humidity, the plants are kept for 16 days at 23° C. and 60% relative humidity in a greenhouse. The percentage leaf area covered by disease is assessed 18 days after inoculation. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-3 Action Against Pyricularia oryzae (Causal Fungus of Blast on Rice) a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 3 days. The fungicide interactions in the combinations are calculated according to the COLBY method.

b) Protective Treatment of Leaf Pieces

Rice leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 4 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-4 Action Against Alternaria solani (Causal Fungus of Early Blight on Tomato) a) Fungal Growth Assay

Conidia—harvested from a freshly grown colony—of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 48 hrs. The fungicide interactions in the combinations are calculated according to the COLBY method.

b) Protective Treatment of Whole Plants

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (2×10⁵ conidia/ml) on the test plants. After an incubation period of 3 days at 20° C. and 95% relative humidity in a growth chamber the percentage leaf area covered by disease is assessed. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-5 Action Against Pyrenophora teres (Causal Fungus of Net Blotch on Barley) a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 2 days. The fungicide interactions in the combinations are calculated according to the COLBY method. The data generated in this experiment indicate synergy between cyprodinil and pyribencarb when used in mixture with one another.

Control of Pyrenophora teres Dosage in mg active ingredient/liter final medium Observed Expected Synergistic control control benefit in Cyprodinil Pyribencarb in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 0.25 — 52.0 — — 0.5 — 59.0 — — — 0.004 0 — — — 0.008 0 — — — 0.016 0 — — — 0.031 0 — — — 0.063 17.0 — — 0.5 0.008 69.5 59.0 +10.5 0.25 0.004 64.3 52.0 +12.3 0.5 0.016 80.0 59.0 +21.0 0.25 0.008 66.8 52.0 +14.8 0.5 0.031 79.3 59.0 +20.3 0.25 0.016 74.6 52.0 +22.6 0.5 0.063 79.2 65.9 +13.3 0.25 0.031 76.9 52.0 +24.9

b) Protective Treatment of Leaf Pieces

Barley leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 4 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-6 Action Against Venturia inaequalis (Causal Fungus of Scab on Apple) a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 12 days. The fungicide interactions in the combinations are calculated according to the COLBY method.

b) Protective Treatment of Whole Plants

4 week old apple seedlings cv. McIntosh are treated with the formulated test compound in a spray chamber. One day after application, the apple plants are inoculated by spraying a spore suspension (4×10⁵ conidia/ml) on the test plants. After an incubation period of 4 days at 21° C. and 95% relative humidity the plants are placed for 4 days at 21° C. and 60% relative humidity in a greenhouse. After another 4 day incubation period at 21° C. and 95% relative humidity the percentage leaf area covered by disease is assessed. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-7 Action Against Leptosphaeria nodorum (Causal Fungus of Wheat Glume Blotch) a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 2 days. The fungicide interactions in the combinations are calculated according to the COLBY method.

b) Protective Treatment of Leaf Pieces

Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 4 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to the COLBY method.

c) Protective Treatment of Whole Plants

1 week old wheat plants cv. Arina are treated with the formulated test compound in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (5×10⁵ spores/ml) on the test plants. After an incubation period of 1 day at 20° C. and 95% relative humidity the plants are kept for 10 days at 20° C. and 60% relative humidity in a greenhouse. The percentage leaf area covered by disease is assessed 11 days after inoculation. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-8 Action Against Pseudocercosporella herpotrichoides var. acuformis (Causal Fungus of Eyespot Disease in Cereals)—Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C and the inhibition of growth is determined photometrically after 3 days. The fungicide interactions in the combinations are calculated according to the COLBY method. The data generated in this experiment indicate synergy between cyprodinil and boscalid, cyprodinil and dodine and cyprodinil and pyribencarb when used in mixture with one another.

Control of Pseudocercosporella herpotrichoides var. acuformis Dosage in mg active ingredient/liter final medium Observed Expected Synergistic control control benefit in Cyprodinil Boscalid in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 0.0625 — 23.5 — — 0.125 — 40.7 — — 0.25 — 28.9 — — 0.5 — 19.6 — — 1 — 17.5 — — 2 — 24.6 — — 4 — 33.6 — — — 0.031 0 — — — 0.063 2.5 — — — 0.125 32.8 — — — 0.25 58.4 — — — 0.5 77.1 — — 4 0.25 95.3 72.4 +22.9 2 0.125 91.4 49.4 +42.0 1 0.063 67.6 19.6 +48.0 0.5 0.031 46.7 19.6 +27.1 4 0.5 95.9 84.8 +11.1 2 0.25 95.2 68.6 +26.6 1 0.125 88.5 44.6 +43.9 0.5 0.063 68.7 21.6 +47.1 0.25 0.031 45.2 28.9 +16.3 2 0.5 95.9 82.7 +13.2 1 0.25 93.8 65.7 +28.1 0.5 0.125 86.3 46.0 +40.3 0.25 0.063 65.7 30.7 +35.0 1 0.5 94.8 81.1 +13.7 0.5 0.25 94.8 66.5 +28.3 0.25 0.125 86.6 52.2 +34.4 0.125 0.063 57.1 42.2 +14.9 0.0625 0.031 40.1 23.5 +16.6 0.5 0.5 95.8 81.6 +14.2 0.25 0.25 92.2 70.4 +21.8 0.125 0.125 79.7 60.2 +19.5 0.0625 0.063 66.3 25.4 +40.9 Observed Expected Synergistic control control benefit in Cyprodinil Dodine in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 0.125 — 10.9 — — 0.25 — 14.8 — — 0.5 — 13.7 — — 1 — 17.9 — — 2 — 20.3 — — 4 — 25.9 — — 8 — 33.6 — — 16 — 46.2 — — — 0.125 0 — — — 0.25 0 — — — 0.5 0 — — — 1 0 — — — 2 1.4 — — — 4 31.3 — — — 8 70.5 — — — 16 72.4 — — 8 4 71.3 54.4 +16.9 4 2 46.8 26.9 +19.9 2 1 23.3 20.3 +3.0 1 0.5 37.0 17.9 +19.1 0.5 0.25 25.7 13.7 +12.0 0.25 0.125 31.2 14.8 +16.4 16 16 97.2 85.1 +12.1 8 8 84.8 80.4 +4.4 4 4 69.1 49.0 +20.1 2 2 33.8 21.4 +12.4 1 1 28.3 17.9 +10.4 2 4 64.3 45.2 +19.1 1 2 40.2 19.1 +21.1 0.5 1 30.0 13.7 +16.3 0.25 0.5 21.6 14.8 +6.8 0.125 0.25 33.4 10.9 +22.5 Observed Expected Synergistic control control benefit in Cyprodinil Pyribencarb in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 0.125 — 16.6 — — 0.5 — 30.1 — — 1 — 19.3 — — 2 — 21.5 — — 4 — 27.2 — — — 0.008 16.2 — — — 0.016 40.1 — — — 0.031 61.1 — — 4 0.031 86.7 71.6 +15.1 2 0.016 67.4 53.0 +14.4 1 0.008 52.3 32.4 +19.9 2 0.031 86.9 69.4 +17.5 1 0.016 61.0 51.7 +9.3 0.5 0.008 55.2 41.4 +13.8 1 0.031 80.2 68.6 +11.6 0.125 0.008 50.2 30.1 +20.1

Example B-9 Action Against Ustilago maydis (Causal Fungus of Corn Smut)—Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 2 days. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-10 Action Against Erysiphe graminis f. sp. hordei (Causal Fungus of Barley Powdery Mildew) on Barley a) Protective Treatment of Leaf Pieces

Barley leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated by dusting with spores of the fungus. After appropriate incubation the activity of a compound is assessed 5 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to the COLBY method.

b) Protective Treatment of Whole Plants

1 week old barley plants cv. Regina are treated with the formulated test compound in a spray chamber. One day after application, the barley plants are inoculated by shaking powdery mildew infected plants above the test plants. After an incubation period of 6 days at 20° C./18° C. (day/night) and 60% relative humidity in a greenhouse the percentage leaf area covered by disease is assessed. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-11 Action Against Erysiphe graminis f. sp. tritici (Causal Fungus of Wheat Powdery Mildew)—Protective Treatment of Leaf Pieces

Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated by dusting with spores of the fungus. After appropriate incubation the activity of a compound is assessed 6 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-12 Action Against Puccinia recondita (Causal Fungus of Wheat Brown Rust) on Wheat a) Protective Treatment of Leaf Pieces

Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 9 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to the COLBY method.

b) Protective Treatment of Whole Plants

1 week old wheat plants cv. Arina are treated with the formulated test compound in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (1×10⁵ uredospores/ml) on the test plants. After an incubation period of 2 days at 20° C. and 95% relative humidity the plants are kept in a greenhouse for 8 days at 20° C. and 60% relative humidity. The percentage leaf area covered by disease is assessed 10 days after inoculation. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-13 Action Against Podosphaera leucotricha (Causal Fungus of Apple Powdery Mildew) on Apple—Protective Treatment of Whole Plants

5 week old apple seedlings cv. McIntosh are treated with the formulated test compound in a spray chamber. One day after, the treated apple plants are inoculated by shaking plants infected with apple powdery mildew above the test plants. After an incubation period of 12 days at 22° C. and 60% relative humidity under a light regime of 14/10 hours (light/dark) the percentage leaf area covered by disease is assessed. The fungicide interactions in the combinations are calculated according to the COLBY method.

Example B-14 Action Against Fusarium culmorum (Causal Fungus of Wheat Root Rot)—Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C and the inhibition of growth is determined photometrically after 2 days. The fungicide interactions in the combinations are calculated according to the COLBY method. The data generated in this experiment indicate synergy between cyprodinil and dodine, cyprodinil and fluazinam and cyprodinil and pyribencarb when used in mixture with one another.

Control of Fusarium culmorum Dosage in mg active ingredient/liter final medium Observed Expected Synergistic control control benefit in Cyprodinil Dodine in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 4 — 0 — — 8 — 0 — — 16 — 6.7 — — 32 — 26.9 — — — 8 3.3 — — — 16 15.1 — — 32 16 98.0 38.0 +60.0 16 8 96.3 9.8 +86.5 16 16 98.0 20.8 +77.2 8 8 80.8 3.3 +77.5 8 16 98.0 15.1 +82.9 4 8 46.3 3.3 +43.0 4 16 97.6 15.1 +82.5 Observed Expected Synergistic control control benefit in Cyprodinil Fluazinam in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 2 — 0 — — 4 — 0 — — 8 — 0 — — 16 — 9.8 — — 32 — 16.4 — — — 0.063 5.1 — — — 0.125 11.8 — — — 0.25 27.4 — — — 0.5 35.7 — — — 1 72.4 — — 32 0.25 96.0 39.3 +56.7 32 0.5 97.7 46.2 +51.5 16 0.25 83.4 34.5 +48.9 8 0.125 17.3 11.8 +5.5 4 0.063 19.5 5.1 +14.4 32 1 97.9 77.0 +20.9 16 0.5 96.2 42.0 +54.2 8 0.25 36.6 27.4 +9.2 4 0.125 20.1 11.8 +8.3 2 0.063 21.5 5.1 +16.4 16 1 96.4 75.1 +21.3 8 0.5 74.3 35.7 +38.6 8 1 96.9 72.4 +24.5 4 0.5 63.6 35.7 +27.9 Observed Expected Synergistic control control benefit in Cyprodinil Pyribencarb in % in % % control (ppm ai) (ppm ai) (% C_(obs)) (% C_(exp)) % C_(obs) − % C_(exp) [mg/L] [mg/L] observed expected difference 8 — 2.4 — — 16 — 8.4 — — 32 — 21.7 — — — 0.125 0 — — — 0.25 8.7 — — — 0.5 11.5 — — — 1 16.2 — — 32 0.25 75.2 28.5 +46.7 16 0.125 19.9 8.4 +11.5 32 0.5 85.3 30.7 +54.6 16 0.25 37.4 16.4 +21.0 32 1 88.4 34.4 +54.0 16 0.5 49.3 18.9 +30.4 8 0.25 23.8 10.9 +12.9 16 1 55.3 23.3 +32.0 8 0.5 26.0 13.6 +12.4 8 1 31.4 18.2 +13.2

Example B-15 Action Against Uncinula necator (Causal Fungus of Grape Powdery Mildew) on Grapevines—Protective Treatment of Whole Plants

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 26° C. and 60% relative humidity under a light regime of 14/10 hours (light/dark) the percentage leaf area covered by disease is assessed. The fungicide interactions in the combinations are calculated according to the COLBY method.

The combinations according to the invention exhibit good activity in all of the above examples. 

What is claimed is:
 1. A composition for control of phytopathogenic diseases on useful plants or on propagation material thereof, that comprises as active ingredient a mixture of component (A) and a synergistically effective amount of component (B), wherein component (A) is Cyprodinil; and component (B) is a compound of formula A-2


2. A composition according to claim 1; wherein a weight ratio of component (A) to component (B) is from 2000:1 to 1:1000.
 3. A method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to claim
 1. 4. A method of controlling phytopathogenic diseases on useful plants, which comprises applying to the useful plants or the locus thereof a composition according to claim
 1. 5. A method according to claim 4, wherein the useful plants are cereal plants.
 6. A method according to claim 4, wherein the useful plants are fruit plants or vegetable plants.
 7. A method according to claim 4, wherein the useful plants are grape plants.
 8. A method of protecting natural substances of plant origin, which have been taken from the natural life cycle, which comprises applying to said natural substances of plant origin or their processed forms a composition according to claim
 1. 9. A composition according to claim 1, wherein Cyprodinil is present as (i) a salt of Cyprodinil or (ii) a metal complex of Cyprodinil.
 10. A composition according to claim 2, wherein the weight ratio of component (A) to component (B) is from 100:1 and 1:100.
 11. A composition according to claim 10, wherein the weight ratio of component (A) to component (B) is from 20:1 and 1:50.
 12. A method according to claim 4, wherein the useful plants are wheat plants.
 13. A method according to claim 4, wherein the step of applying comprises applying Cyprodinil at a rate of 5 to 2000 g a.i./ha and the compound of formula A-2 at a rate of 1 to 5000 g a.i./ha.
 14. A method according to claim 4, wherein the step of applying comprises applying from 20 to 4000 g of the composition per hectare. 